Calcium salts-supported metal catalyst, method for preparing the same, and method for hydrodeoxygenation reaction of oxygenates using the same

ABSTRACT

Disclosed herein are a calcium salts-supported metal catalyst, a method for preparing the same, and a method for the hydrodeoxygenation reaction of oxygenates using the same. The catalyst, in which a metal catalyst is supported on a carrier of a calcium salt, for example, calcium carbonate, has the effect of increasing the efficiency of hydrodeoxygenation reaction of oxygenates.

BACKGROUND OF THE INVENTION Field of the Invention

Disclosed herein are a metal catalyst supported on a calcium salt suchas calcium carbonate, a method for preparing the same, and a method forthe hydrodeoxygenation reaction of oxygenates using the same.

EXPLANATION ON NATIONALLY SUPPORTED RESEARCH AND DEVELOPMENT

This research has been carried out under the supervision of the KoreaInstitute of Science and Technology with the support of the Ministry ofTrade, Industry and Energy (specialized organization for researchmanagement: Korea Institute of Energy Technology Evaluation andPlanning, title of research project: Development of Catalytic ChemicalReaction Technique for High-Carbon Transport Fuelization of Furan-basedCompounds Derived from Unfermented Sugar, project assignment number:1415154087).

Description of the Related Art

Woody biomass, including wood and herbs, is presented as a potentiallysustainable source of raw materials for the production of biofuels andsubstitute chemicals for petroleum, and these biofuels and chemicals canbe obtained through thermochemical processes such as pyrolysis.Thermochemical processes including pyrolysis and liquefaction are widelystudied chemical processes. Pyrolysis oils is environmentally friendlycompared to fossil fuels because it can be obtained from renewablesources. However, high oxygen concentrations inhibit the direct use ofthis biofuel. In addition, thermal instability and difficulty in storageof bio-oils are major obstacles to the widespread use of bio-oils. Inorder to convert bio-oils to petroleum-like fuels, biomass pyrolysisoils must be stabilized and oxygen atoms must be removed therefrom.

Hydrodeoxygenation (HDO) reaction is one of the processes frequentlyused to convert biofuels to petroleum-like deoxygenated hydrocarbonfuels. The hydrodeoxygenation reaction allows to obtain an oil withsignificantly improved fuel properties, including stabilization and highenergy density. Although there are not many actual cases of catalyticchemical conversion of biomass pyrolysis oils, systematic researchesinvolving biomass pyrolysis oils and catalysts and using model compoundshave become very active. It is well known that in the development ofcatalysts for hydrodeoxygenation reaction, the interaction betweenreactants and catalysts affects the hydrodeoxygenation reaction.Catalyst carriers can improve the catalytic activity forhydrodeoxygenation reaction depending on the state of the reaction. Forexample, a lot of studies on HDO reaction have been conducted fortransition metal or noble metal catalysts using solid acids such assilica and alumina as the carrier. Also, in addition to these solidacid-based catalysts, MgO-supported catalysts have been applied to thehydrodeoxygenation reaction.

CITATION LIST Patent Literature

Patent Literature 1: Korean Patent Laid-Open No. 10-2013-0017250

SUMMARY OF THE INVENTION

In one aspect, an object of the present disclosure is to provide acatalyst for the hydrodeoxygenation reaction of oxygenates.

In another aspect, an object of the present disclosure is to provide amethod for preparing the catalyst for hydrodeoxygenation reaction.

In yet another aspect, an object of the present disclosure is to providea method for the hydrodeoxygenation reaction of oxygenates using thecatalyst for hydrodeoxygenation reaction.

In one aspect, the technology disclosed herein provides a catalyst forhydrodeoxygenation reaction comprising a carrier comprising a calciumsalt, and a metal catalyst supported on the carrier.

In one exemplary embodiment, the calcium salt may comprise at least oneselected from the group consisting of calcium chloride, calciumfluoride, calcium hydroxide, calcium carbonate, calcium nitrate, calciumacetate, calcium citrate, calcium lactate, calcium phosphate, calciumgluconate, calcium sulfate, and calcium iodate.

In one exemplary embodiment, the calcium salt may comprise calciumcarbonate.

In one exemplary embodiment, the catalyst for hydrodeoxygenationreaction may remove the oxygen atoms of oxygenates.

In one exemplary embodiment, the oxygenates may be oxygen-containinghydrocarbon compounds having 5 to 20 carbon atoms.

In one exemplary embodiment, the oxygenates may comprise at least oneselected from the group consisting of phenol, alcohol, aldehyde, ketone,ether, and ester.

In one exemplary embodiment, the metal catalyst may comprise at leastone selected from the group consisting of nickel (Ni), cobalt (Co),copper (Cu), platinum (Pt), palladium (Pd), rhodium (Rh), and ruthenium(Ru).

In one exemplary embodiment, the metal catalyst may comprise ruthenium(Ru).

In one exemplary embodiment, the content of the metal catalyst may be0.01 to 50% by weight based on the total weight of the catalyst forhydrodeoxygenation reaction.

In another aspect, the technology disclosed herein provides a method forpreparing the catalyst for hydrodeoxygenation reaction, comprising thesteps of: (1) mixing a solution of a metal catalyst precursor with acarrier comprising a calcium salt to impregnate it; and (2) firing thecarrier impregnated with the solution of a metal catalyst precursor.

In one exemplary embodiment, the firing may be carried out in an airatmosphere at 100 to 500° C.

In another aspect, the technology disclosed herein provides a method forthe hydrodeoxygenation reaction of oxygenates, comprising the step ofapplying the catalyst for hydrodeoxygenation reaction to oxygenates toremove the oxygen atoms of the oxygenates.

In one exemplary embodiment, the reaction method may comprise the stepsof: introducing the catalyst for hydrodeoxygenation reaction, theoxygenate and hydrogen gas into a reactor; and heating the reactor tocarry out the hydrodeoxygenation reaction of the oxygenate.

In one exemplary embodiment, the hydrogen gas may be introduced at apressure of 10 to 100 bar at room temperature.

In one exemplary embodiment, the hydrodeoxygenation reaction may becarried out at 100 to 500° C.

The technology disclosed herein provides a catalyst for thehydrodeoxygenation reaction of oxygenates.

The metal catalyst supported on a calcium salt carrier according to thepresent invention increases the efficiency of hydrodeoxygenationreaction of oxygenates.

In another aspect, the technology disclosed herein provides a method forpreparing the catalyst for hydrodeoxygenation reaction.

In yet another aspect, the technology disclosed herein provides a methodfor the hydrodeoxygenation reaction of oxygenates using the catalyst forhydrodeoxygenation reaction.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the reactants and products of the hydrodeoxygenationreaction according to one embodiment of the present invention;

FIG. 2 is a TEM photograph of a ruthenium catalyst supported on calciumcarbonate according to one embodiment of the present invention;

FIG. 3 compares the hydrodeoxygenation reaction results of variouscatalysts; and

FIG. 4 shows the hydrodeoxygenation reaction results when ahydrodeoxygenation reaction was carried out using a catalyst forhydrodeoxygenation reaction according to one embodiment of the presentinvention and then the catalyst was washed, dried, and reused.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the present invention will be described in detail.

In one aspect, the technology disclosed herein provides a catalyst forhydrodeoxygenation reaction comprising a carrier comprising a calciumsalt, and a metal catalyst supported on the carrier.

In another aspect, the technology disclosed herein provides a catalystfor hydrodeoxygenation reaction comprising a carrier consisting of acalcium salt, and a metal catalyst supported on the carrier.

In one exemplary embodiment, the calcium salt may comprise at least oneselected from the group consisting of calcium chloride, calciumfluoride, calcium hydroxide, calcium carbonate, calcium nitrate, calciumacetate, calcium citrate, calcium lactate, calcium phosphate, calciumgluconate, calcium sulfate, and calcium iodate.

In another aspect, the technology disclosed herein provides a catalystfor hydrodeoxygenation reaction comprising a carrier comprising calciumcarbonate (CaCO₃), and a metal catalyst component supported on thecarrier.

In another aspect, the technology disclosed herein provides a catalystfor hydrodeoxygenation reaction comprising a carrier consisting ofcalcium carbonate (CaCO₃), and a metal catalyst component supported onthe carrier.

The crystallinity of the calcium carbonate carrier is not limited, andthe appearance shape of the calcium carbonate carrier, such as powder orpellet, may not be limited.

In one exemplary embodiment, the catalyst for hydrodeoxygenationreaction may allow to prepare deoxygenated compounds from oxygenates.

The catalyst for hydrodeoxygenation reaction according to the presentdisclosure improves the reactivity of oxygenates to hydrodeoxygenationby using a calcium salt as a carrier and thereby achieves a highhydrodeoxygenation reaction efficiency.

As used herein, the term “oxygenate” refers to a compound that containsan oxygen atom within the molecular structure.

As used herein, the term “deoxygenated compound” refers to a compoundobtained by removing the oxygen contained in an oxygenate. It may referto a compound that does not contain an oxygen atom within the molecularstructure.

In one exemplary embodiment, the oxygenate may comprise at least oneselected from the group consisting of phenol, alcohol, aldehyde, ketone,ether, and ester.

In one exemplary embodiment, the oxygenate may be an oxygen-containinghydrocarbon compound.

In one exemplary embodiment, the oxygenate may be an oxygen-containingaromatic hydrocarbon compound.

In one exemplary embodiment, the oxygenate may have 5 to 20 carbonatoms. In another exemplary embodiment, the oxygenate may have 5 ormore, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 ormore, 12 or more, 13 or more, 14 or more, or 15 or more carbon atoms. Inanother exemplary embodiment, the oxygenate may have 20 or less, 19 orless, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 orless, 12 or less, 11 or less, or 10 or less carbon atoms.

In one exemplary embodiment, the oxygenate may be a degradation productproduced by thermal, chemical, or biological degradation of an organicmaterial including an organic polymer.

In one exemplary embodiment, the oxygenate may be a degradation productproduced by thermal, chemical, or biological degradation of biomassincluding wood, herbs, and algae.

In one exemplary embodiment, the oxygenate may be obtained frompyrolysis oil of woody biomass.

In one exemplary embodiment, the oxygenate may be a lignin monomer.

In one exemplary embodiment, the oxygenate may be eugenol.

In one exemplary embodiment, the deoxygenated compound may be at leastone of methyl chlorohexane and propyl chlorohexane.

In one exemplary embodiment, the metal catalyst may comprise at leastone selected from the group consisting of nickel (Ni), cobalt (Co),copper (Cu), platinum (Pt), palladium (Pd), rhodium (Rh), and ruthenium(Ru).

In one exemplary embodiment, it is preferable, in terms of thehydrodeoxygenation reaction efficiency of the catalyst according to thepresent disclosure, that the metal catalyst comprise ruthenium (Ru).

In one exemplary embodiment, the metal catalyst may be formed from atleast one metal precursor selected from the group consisting of a nickel(Ni) precursor, a cobalt (Co) precursor, a copper (Cu) precursor, aplatinum (Pt) precursor, a palladium (Pd) precursor, a rhodium (Rh)precursor, and a ruthenium (Ru) precursor.

In one exemplary embodiment, the metal precursor may be at least oneselected from the group consisting of a metal salt compound, a metalacetate compound, a metal halide compound, a metal nitrate compound, ametal hydroxide compound, a metal carbonyl compound, a metal sulfatecompound, and a fatty acid metal salt compound.

In one exemplary embodiment, the metal precursor may be a metal chlorideor a metal chlorate.

In one exemplary embodiment, the content of the metal catalyst may be0.01 to 50% by weight based on the total weight of the catalyst forhydrodeoxygenation reaction. In another exemplary embodiment, thecontent of the metal catalyst may be 0.01% by weight or more, 0.1% byweight or more, 1% by weight or more, 3% by weight or more, 5% by weightor more, 7% by weight or more, or 10% by weight or more based on thetotal weight of the catalyst for hydrodeoxygenation reaction. In yetanother exemplary embodiment, the content of the metal catalyst may be50% by weight or less, 45% by weight or less, 40% by weight or less, 35%by weight or less, 30% by weight or less, 25% by weight or less, 20% byweight or less, 15% by weight or less, 10% by weight or less, 7% byweight or less, or 5% by weight or less based on the total weight of thecatalyst for hydrodeoxygenation reaction. For example, it is preferable,in terms of the activity of hydrodeoxygenation reaction and theefficiency of the catalyst, that the content of the metal catalyst be 3to 10% by weight based on the total weight of the catalyst forhydrodeoxygenation reaction.

In another aspect, the technology disclosed herein provides a method forpreparing a catalyst for hydrodeoxygenation reaction, comprising thesteps of: (1) mixing a solution of a metal catalyst precursor with acarrier comprising a calcium salt to impregnate it; and (2) firing thecarrier impregnated with the solution of a metal catalyst precursor.

In one exemplary embodiment, step (1) may comprise the step ofdissolving a metal catalyst precursor in ion-exchanged water and thenmixing the resultant with a carrier comprising a calcium salt.

In one exemplary embodiment, step (2) may comprise the step of dryingthe carrier impregnated with the solution of a metal catalyst precursorand then firing and reducing it.

In one exemplary embodiment, the firing may be carried out in an airatmosphere at 100 to 500° C. In another exemplary embodiment, the firingmay be carried out at a temperature of 100° C. or more, 150° C. or more,200° C. or more, 250° C. or more, or 300° C. or more. In yet anotherexemplary embodiment, the firing may be carried out at a temperature of500° C. or less, 450° C. or less, 400° C. or less, 350° C. or less, 300°C. or less, or 250° C. or less.

In one exemplary embodiment, the firing may be carried out for 1 to 10hours.

In another aspect, the technology disclosed herein provides a method forthe hydrodeoxygenation reaction of oxygenates, comprising the step ofapplying a catalyst for hydrodeoxygenation reaction to oxygenates toremove the oxygen atoms of the oxygenates.

In one exemplary embodiment, the reaction method may comprise the stepsof: introducing the catalyst for hydrodeoxygenation reaction, theoxygenate and hydrogen gas into a reactor; and heating the reactor tocarry out the hydrodeoxygenation reaction of the oxygenate.

In one exemplary embodiment, the reactor may be a batch reactor.

In one exemplary embodiment, an inert gas of nitrogen or helium may ormay not be introduced into the reactor.

In one exemplary embodiment, the hydrogen gas may be introduced at apressure of 10 to 100 bar at room temperature. In another exemplaryembodiment, the hydrogen gas may be introduced at a pressure of 10 baror more, 20 bar or more, 30 bar or more, 40 bar or more, or 50 bar ormore at room temperature. In yet another exemplary embodiment, thehydrogen gas may be introduced at a pressure of 100 bar or less, 90 baror less, 80 bar or less, 70 bar or less, 60 bar or less, or 50 bar orless at room temperature.

In one exemplary embodiment, the hydrodeoxygenation reaction may becarried out at 100 to 500° C. In another exemplary embodiment, thehydrodeoxygenation reaction may be carried out at a temperature of 100°C. or more, 150° C. or more, 200° C. or more, 250° C. or more, or 300°C. or more. In yet another exemplary embodiment, the hydrodeoxygenationreaction may be carried out at a temperature of 500° C. or less, 450° C.or less, 400° C. or less, 350° C. or less, 300° C. or less, or 250° C.or less. If the temperature is less than, for example, 100° C., there isalmost no hydrodeoxygenation reaction activity. If the temperature ishigher than 500° C., it is difficult to operate the reactor due to thehigh temperature and high pressure, and rapid deactivation of thecatalyst may occur. Thus, the hydrodeoxygenation reaction of oxygenatesmay preferably be carried out at 200 to 500° C. or at 250 to 400° C.

Hereinafter, the present invention will be described in detail by way ofexamples. It will be apparent to those skilled in the art that theseexamples are for illustrative purposes only, and the scope of thepresent invention is not construed as being limited by these examples.

Example 1

In order to prepare 5% by weight of Ru/CaCO₃, 10.3 g of RuCl₃ was mixedwith 50 g of ion-exchanged water and completely dissolved, and then theresultant was mixed with 95 g of calcium carbonate or other carriers.The mixture was stirred for 30 minutes, dried at 90° C. for 16 hours andthen fired at 400° C. for 2 hours in an air atmosphere. Thereafter, themixture was reduced by flowing 5% Ha/Ar mixed gas at 400° C. for 4hours. Catalysts comprising 5% by weight of Ru were prepared by the samemethod using magnesium oxide (MgO), magnesium-aluminum mixed oxide(MgAlO_(x)), hydrotalcite (HT), and zirconia (ZrO₂) as the othercarriers.

Test Example 1

Hydrodeoxygenation reaction was carried out using the catalysts preparedin Example 1 and a batch reactor. Eugenol (CAS 97-53-0) was used as areactant. 0.003 mol of eugenol, 30 mL of n-hexadecane, and 0.05 g of acatalyst were introduced into an autoclave reactor (internal volume ofabout 160 mL) at room temperature, which was then filled with 50 bar ofhydrogen gas at room temperature. The reactor was heated to 250° C.,followed by stirring at 800 rpm for 1 hour to carry out the reaction.The reactor was cooled back to room temperature and then the liquidreaction product was analyzed.

FIG. 1 shows the reactants and products of the hydrodeoxygenationreaction. A product having no oxygen atom (0-O), a product having oneoxygen atom (1-0), and a product having two oxygen atoms (2-O) wereobtained from eugenol, which has two oxygen atoms. As shown in FIG. 3,when CaCO₃ was used as the carrier, the yield of the product having twooxygen atoms (2-O) was lower and the yield of the product having nooxygen atom (0-O) was higher than the various basic carriers, includingMgO, Mg—Al mixed oxide (MgAlO_(x)), hydrotalcite (HT), and zirconia(ZrO₂), which indicates that the carrier significantly increased thehydrodeoxygenation reaction activity. When CaCO₃ was used as thecarrier, the yield of 1-0 was about 25% higher than the case of using azirconia carrier, and the yield of 2-0, which did not go throughhydrodeoxygenation reaction, was about 30% lower than the case of usinga zirconia carrier, which indicates that the carrier increased thehydrodeoxygenation reaction efficiency.

Also, when the catalyst, after reaction, was washed, dried and reused,the hydrodeoxygenation reaction activity was maintained without asignificant change even in the third use of the catalyst, and thehydrodeoxygenation reaction activity was remarkably higher than those offresh catalysts using a carrier of MgO, Mg—Al mixed oxide (MgAlO_(x)) orhydrotalcite (HT) (see FIG. 4).

While the present invention has been described with respect to thespecific embodiments, it will be apparent to those skilled in the artthat the above descriptions are only preferred embodiments and that thescope of the present invention is not limited thereto. Thus, the scopeof the present invention should be defined by the appended claims andequivalents thereof.

What is claimed is:
 1. A catalyst for hydrodeoxygenation reactioncomprising a carrier comprising a calcium salt, and a metal catalystsupported on the carrier.
 2. The catalyst for hydrodeoxygenationreaction according to claim 1, wherein the calcium salt comprises atleast one selected from the group consisting of calcium chloride,calcium fluoride, calcium hydroxide, calcium carbonate, calcium nitrate,calcium acetate, calcium citrate, calcium lactate, calcium phosphate,calcium gluconate, calcium sulfate, and calcium iodate.
 3. The catalystfor hydrodeoxygenation reaction according to claim 2, wherein thecalcium salt comprises calcium carbonate.
 4. The catalyst forhydrodeoxygenation reaction according to claim 1, wherein the catalystfor hydrodeoxygenation reaction removes the oxygen atoms of oxygenates.5. The catalyst for hydrodeoxygenation reaction according to claim 4,wherein the oxygenates are oxygen-containing hydrocarbon compoundshaving 5 to 20 carbon atoms.
 6. The catalyst for hydrodeoxygenationreaction according to claim 4, wherein the oxygenates comprise at leastone selected from the group consisting of phenol, alcohol, aldehyde,ketone, ether, and ester.
 7. The catalyst for hydrodeoxygenationreaction according to claim 1, wherein the metal catalyst comprises atleast one selected from the group consisting of nickel (Ni), cobalt(Co), copper (Cu), platinum (Pt), palladium (Pd), rhodium (Rh), andruthenium (Ru).
 8. The catalyst for hydrodeoxygenation reactionaccording to claim 7, wherein the metal catalyst comprises ruthenium(Ru).
 9. The catalyst for hydrodeoxygenation reaction according to claim1, wherein the content of the metal catalyst is 0.01 to 50% by weightbased on the total weight of the catalyst for hydrodeoxygenationreaction.
 10. A method for preparing the catalyst for hydrodeoxygenationreaction according to claim 1, comprising the steps of: (1) mixing asolution of a metal catalyst precursor with a carrier comprising acalcium salt to impregnate it; and (2) firing the carrier impregnatedwith the solution of a metal catalyst precursor.
 11. The method forpreparing the catalyst for hydrodeoxygenation reaction according toclaim 10, wherein the firing is carried out in an air atmosphere at 100to 500° C.
 12. A method for hydrodeoxygenation reaction of oxygenates,comprising the step of applying the catalyst for hydrodeoxygenationreaction according to claim 1 to oxygenates to remove the oxygen atomsof the oxygenates.
 13. The method for hydrodeoxygenation reaction ofoxygenates according to claim 12, comprising the steps of: introducingthe catalyst for hydrodeoxygenation reaction, the oxygenate and hydrogengas into a reactor; and heating the reactor to carry out thehydrodeoxygenation reaction of the oxygenate.
 14. The method forhydrodeoxygenation reaction of oxygenates according to claim 13, whereinthe hydrogen gas is introduced at a pressure of 10 to 100 bar at roomtemperature.
 15. The method for hydrodeoxygenation reaction ofoxygenates according to claim 13, wherein the hydrodeoxygenationreaction is carried out at 100 to 500° C.